EP2475692B1 - Verfahren zur herstellung einer wässrigen bindemitteldispersion - Google Patents

Verfahren zur herstellung einer wässrigen bindemitteldispersion Download PDF

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EP2475692B1
EP2475692B1 EP20100771369 EP10771369A EP2475692B1 EP 2475692 B1 EP2475692 B1 EP 2475692B1 EP 20100771369 EP20100771369 EP 20100771369 EP 10771369 A EP10771369 A EP 10771369A EP 2475692 B1 EP2475692 B1 EP 2475692B1
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weight
monomer
aqueous
monomers
process according
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EP2475692A1 (de
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Kevin MÜLLER
Kathrin Michl
Christian Brand
Kai Olfermann
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/066—Copolymers with monomers not covered by C08L33/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix

Definitions

  • the present invention is a process for preparing an aqueous dispersion of a polymer A by free-radically initiated aqueous emulsion polymerization of ethylenically unsaturated monomers in the presence of at least one dispersing aid and at least one radical initiator, which is characterized in that the polymerization 0.1 to 5% by weight Acrylamide and / or methacrylamide (monomer A1), 0.1 to 15% by weight at least one ethylenically unsaturated C 3 - to C 6 -mono- or dicarboxylic acid (monomer A 2), 0.1 to 10% by weight at least one ethylenically unsaturated compound having at least one oxiranyl or oxetanyl group (monomer A3), and 70 to 99.7% by weight at least one other ethylenically unsaturated compound which is copolymerizable with the monomers A1 to A3 (monomer A4), can be used, wherein the amounts of mono
  • the present invention furthermore relates to aqueous polymer dispersions obtained by the process according to the invention, the use of these aqueous polymer emulsion dispersions as binders for granular and / or fibrous substrates, processes for the production of moldings using the aqueous dispersion of polymer dispersion according to the invention and those obtainable by the process according to the invention Shaped body itself.
  • binders which contain formaldehyde-releasing crosslinkers. But there is the danger of unwanted formaldehyde emission.
  • sheets of particulate materials such as glass fibers are known in which mixtures of high molecular weight polycarboxylic acids and polyhydric alcohols, alkanolamines or polyhydric amines act as binders.
  • binders for the production of fiber webs, in particular glass fiber webs known.
  • the binders contain a polycarboxylic acid having at least two carboxylic acid groups and optionally also anhydride groups and a polyol.
  • These binders require a phosphorus-containing reaction accelerator to achieve sufficient strengths of the glass fiber webs. It should be noted that the presence of such a reaction accelerator can only be dispensed with if a highly reactive polyol is used. As highly reactive polyols ⁇ -hydroxyalkylamides are mentioned.
  • the EP-A-651088 describes corresponding binders for substrates made of cellulose fiber. These binders necessarily contain a phosphorus-containing reaction accelerator.
  • the EP-A-672 920 describes formaldehyde-free binding, impregnating or coating compositions which comprise a polymer which is composed of 2 to 100% by weight of an ethylenically unsaturated acid or an acid anhydride as comonomer and contains at least one polyol.
  • the polyols are substituted triazine, triazinetrione, benzene or cyclohexyl derivatives, the polyol radicals always being in the 1,3,5-position of the mentioned rings.
  • the DE-A-2214450 describes a copolymer which is composed of 80 to 99% by weight of ethylene and 1 to 20% by weight of maleic anhydride.
  • the copolymer is used, together with a crosslinking agent, in powder form or in dispersion in an aqueous medium for surface coating.
  • a crosslinking agent an amino group-containing polyhydric alcohol is used.
  • it must be heated up to 300 ° C.
  • the binder is free of formaldehyde and is obtained by mixing a carboxylic acid group, carboxylic acid anhydride group or carboxylic acid salt group-having polymer and a crosslinking agent.
  • the crosslinker is a ⁇ -hydroxyalkylamide or a polymer or copolymer thereof.
  • the crosslinkable with the ⁇ -hydroxyalkylamide polymer is, for example, composed of unsaturated mono- or dicarboxylic acids, salts of unsaturated mono- or dicarboxylic acids or unsaturated anhydrides.
  • Self-curing polymers are obtained by copolymerization of the ⁇ -hydroxyalkylamides with monomers containing carboxyl groups.
  • the object of the present invention was to provide a formaldehyde-free binder system for granular and / or fibrous substrates, in particular papers, by means of which substrates with an improved bursting pressure result compared with the binders of the prior art.
  • aqueous dispersion of the polymer A (aqueous polymer A dispersion) was found as a binder.
  • monomers A1 acrylamide and / or methacrylamide are used, with methacrylamide being particularly preferred.
  • the amount of the monomers A1 in the process according to the invention is 0.1 to 5 wt .-%, preferably 0.5 to 3 wt .-% and particularly preferably 0.7 to 2.5 wt .-%, each based on the total monomer.
  • ethylenically unsaturated in particular ⁇ , ⁇ -monoethylenically unsaturated C 3 - to C 6 -mono- or dicarboxylic acids are used, where ⁇ , ⁇ -monoethylenically unsaturated C 3 - and C 4 -mono- and C 4 - to C 6 -Dicarboxylic acids are preferred.
  • Suitable monomers A2 are acrylic acid, methacrylic acid, ethylacrylic acid, allylacetic acid, crotonic acid, vinylacetic acid, maleic acid, fumaric acid, itaconic acid, methylmaleic acid, methylenemalonic acid, dimethylacrylic acid and / or 1,2,3,6-tetrahydrophthalic acid and the ammonium, sodium or potassium salts mentioned above acids, with acrylic acid and / or methacrylic acid being particularly preferred.
  • the amount of monomers A2 in the process according to the invention is from 0.1 to 15% by weight, preferably from 0.5 to 10% by weight and more preferably from 1 to 7% by weight, based in each case on the total monomer amount.
  • the monomers A3 used are ethylenic, in particular ⁇ , ⁇ -monoethylenically unsaturated compounds which have at least one oxiranyl or one oxetanyl group, preference being given to those compounds which have an oxiranyl group.
  • Examples of monomers A3 having at least one oxiranyl group are vinyloxirane, allyloxirane, glycidyl acrylate and / or glycidyl methacrylate and as monomers A3 having at least one oxetanyl group vinyloxetane, allyloxetane, 3-methyloxetan-3-ylmethyl acrylate and / or 2-methacrylic acid 3-methyloxetan-3-ylmethylester called.
  • glycidyl acrylate and / or glycidyl methacrylate are used, with glycidyl methacrylate being particularly preferred.
  • the amount of monomers A3 in the process according to the invention is 0.1 to 10 wt .-%, preferably 0.3 to 7 wt .-% and particularly preferably 0.5 to 5 wt .-%, each based on the total monomer.
  • Suitable monomers A4 are in principle all ethylenically unsaturated compounds which differ from the monomers A1 to A3 but are readily copolymerizable with them in a straightforward manner, for example vinylaromatic monomers, such as styrene, ⁇ -methylstyrene, o-chlorostyrene or vinyltoluenes, Vinyl halides, such as vinyl chloride or vinylidene chloride, esters of vinyl alcohol and 1 to 18 carbon atoms monocarboxylic acids, such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, esters of preferably 3 to 6 carbon atoms having ⁇ , ⁇ -monoethylenic unsaturated mono- and dicarboxylic acids, in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, having generally from 1 to 12, preferably 1 to 8 and in particular 1 to 4 carbon atoms alkanol
  • the monomers mentioned generally form the main monomers which, based on the total amount of monomers A4, account for ⁇ 80% by weight, preferably ⁇ 85% by weight and more preferably ⁇ 90% by weight, or even the total amount of the monomers form A4. As a rule, these monomers have only a moderate to low solubility in water under standard conditions [20 ° C., 1 atm (absolute)].
  • Monomers A4 which have an increased water solubility under the abovementioned conditions are those which either have at least one sulfonic acid group and / or their corresponding anion or at least one amino, ureido or N-heterocyclic group and / or their nitrogen-protonated or alkylated Contain ammonium derivatives.
  • Examples which may be mentioned are vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid and its water-soluble salts and N-vinylpyrrolidone, 2-vinylpyridine, 4-vinylpyridine, 2-vinylimidazole, 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-diethylamino) ethyl methacrylate, 2- (N-tert-butylamino) ethyl methacrylate, N- (3-N ', N'-dimethylaminopropyl) methacrylamide and 2- (1-imidazolin-2-onyl) ethyl methacrylate.
  • the abovementioned water-soluble monomers A4 are used only as modifying monomers in amounts of ⁇ 10% by weight, preferably ⁇ 5% by weight and more preferably ⁇ 3% by weight, based in each case on the total amount of monomers A4. However, particularly preferably no such water-soluble monomers A4 are used in the preparation of the polymer A.
  • Monomers A4 which usually increase the internal strength of the films of a polymer matrix, usually have at least two non-conjugated ethylenically unsaturated double bonds.
  • examples include two vinyl radicals containing monomers, two vinylidene radicals having monomers and two alkenyl radicals having monomers.
  • Particularly advantageous are the diesters of dihydric alcohols with ⁇ , ⁇ -monoethylenically unsaturated monocarboxylic acids, among which acrylic and methacrylic acid are preferred.
  • alkylene glycol diacrylates and dimethacrylates such as ethylene glycol diacrylate, 1,2-propylene glycol diacrylate, 1,3-propylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate and ethylene glycol dimethacrylate, 1,2- Propylene glycol dimethacrylate, 1,3-propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate and divinylbenzene, vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl acrylate, diallyl maleate, diallyl fumarate, methylenebisacrylamide, cyclopentadienyl acrylate, triallyl cyanurate or triallyl isocyanurate.
  • alkylene glycol diacrylates and dimethacrylates such as ethylene glycol diacrylate, 1,2-propylene glycol diacryl
  • the abovementioned crosslinking monomers A4 are used in amounts of ⁇ 10% by weight, but preferably in amounts of ⁇ 3% by weight, in each case based on the total amount of monomers A4. However, particularly preferably no such crosslinking monomers A4 are used.
  • Preferred monomers A4 are styrene, n-butyl acrylate, methyl methacrylate, tert-butyl acrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, 2-propylheptyl acrylate and / or 2-ethylhexyl acrylate.
  • methacrylamide as monomer A1 acrylic acid and / or methacrylic acid are advantageously used as monomer A2, glycidyl acrylate and / or glycidyl methacrylate as monomer A3 and styrene, n-butyl acrylate, methyl methacrylate and / or 2-ethylhexyl acrylate as monomer A4.
  • 0.5 to 3% by weight at least one monomer A1 0.5 to 10% by weight at least one monomer A2 and 0.3 to 7% by weight at least one monomer A3 and 80 to 98.7% by weight at least one monomer A4 and especially advantageous 0.7 to 2.5% by weight at least one monomer A1 1 to 7% by weight at least one monomer A2 and 0.5 to 5% by weight at least one monomer A3 and 85.5 to 97.8% by weight at least one monomer A4 used.
  • the total amount of the monomers A1 to A4 can be initially introduced in the aqueous reaction medium before initiation of the polymerization reaction.
  • the metering of the monomers A1 to A4 can be carried out as separate individual streams, as inhomogeneous or homogeneous (part) mixtures or as a monomer emulsion.
  • the monomers A1 to A4 are advantageously metered in the form of a monomer mixture, in particular in the form of an aqueous monomer emulsion.
  • dispersing aids which keep both the monomer droplets and the polymer particles formed dispersed in the aqueous medium and thus ensure the stability of the aqueous polymer dispersion produced are included in the present process.
  • Suitable dispersing agents are both the protective colloids commonly used to carry out free-radical aqueous emulsion polymerizations and emulsifiers.
  • Suitable protective colloids are, for example, polyvinyl alcohols, polyalkylene glycols, alkali metal salts of polyacrylic acids and polymethacrylic acids, gelatin derivatives or acrylic acid, methacrylic acid, maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and / or 4-styrenesulfonic acid-containing copolymers and their alkali metal salts but also N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole, 1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide, amines group-bearing acrylates, methacrylates, acrylamides and / or methacrylamides containing homo- and copolymers.
  • suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromo
  • mixtures of protective colloids and / or emulsifiers can be used.
  • dispersants used are exclusively emulsifiers whose relative molecular weights, in contrast to the protective colloids, are usually below 1000. They may be anionic, cationic or nonionic in nature.
  • anionic emulsifiers are compatible with each other and with nonionic emulsifiers.
  • anionic and cationic emulsifiers are usually incompatible with each other.
  • Common nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 to C 12 ) and also ethoxylated fatty alcohols (EO degree: 3 to 80, alkyl radical: C 8 to C) 36 ).
  • Lutensol® A grades C 12 C 14 fatty alcohol ethoxylates, EO grade: 3 to 8
  • Lutensol® AO grades C 13 C 15 oxo alcohol ethoxylates, EO grade: 3 to 30
  • Lutensol® AT grades C 16 C 18 fatty alcohol ethoxylates, EO grade: 11 to 80
  • Lutensol® ON grades C 10 oxo alcohol ethoxylates, EO grade: 3 to 11
  • Lutensol® TO grades C 13 Oxo alcohol ethoxylates, EO grade: 3 to 20
  • Typical anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C 8 to C 12 ), of sulfuric monoesters of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C 12 to C 18 ) and ethoxylated alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 to C 12 ), of alkylsulfonic acids (alkyl radical: C 12 to C 18 ) and of alkylarylsulfonic acids (alkyl radical: C 9 to C 18 ).
  • alkyl sulfates alkyl radical: C 8 to C 12
  • sulfuric monoesters of ethoxylated alkanols EO degree: 4 to 30, alkyl radical: C 12 to C 18
  • EO degree: 3 to 50 alkyl radical: C 4 to C 12
  • alkylsulfonic acids alkyl radical: C 12
  • R 1 and R 2 are H atoms or C 4 - to C 24 alkyl and are not H atoms at the same time, and M 1 and M 2 may be alkali metal ions and / or ammonium ions have been found suitable.
  • R 1 and R 2 are preferably linear or branched alkyl radicals having 6 to 18 C atoms, in particular having 6, 12 and 16 C atoms or hydrogen, where R 1 and R 2 are not both simultaneously H and Atoms are.
  • M 1 and M 2 are preferably sodium, potassium or Ammonium, with sodium being particularly preferred.
  • Particularly advantageous compounds (I) are those in which M 1 and M 2 are sodium, R 1 is a branched alkyl radical having 12 C atoms and R 2 is an H atom or R 1 .
  • technical mixtures are used which have a proportion of 50 to 90 wt .-% of the monoalkylated product, such as Dowfax® 2A1 (trademark of the Dow Chemical Company).
  • the compounds (I) are generally known, for example from US-A 4269749 , and commercially available.
  • Suitable cationic emulsifiers are generally a primary, secondary, tertiary or quaternary ammonium salt having C 6 -C 18 -alkyl, -alkylaryl or heterocyclic radicals, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and salts of amine oxides, Quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts.
  • Examples include dodecylammonium acetate or the corresponding sulfate, the sulfates or acetates of the various 2- (N, N, N-trimethylammonium) ethylparaffinklaer, N-Cetylpyridiniumsulfat, N-Laurylpyridiniumsulfat and N-cetyl-N, N, N-trimethylammonium sulfate, N- Dodecyl-N, N, N-trimethylammonium sulfate, N-octyl-N, N, N-trimethylammonium sulfate, N, N-distearyl-N, N-dimethylammonium sulfate and the gemini surfactant N, N '- (lauryldimethyl) ethylenediamine disulfate, ethoxylated tallow fatty alkyl N-methylammonium sulfate and ethoxylated oley
  • anionic counter groups are as low as possible nucleophilic, such as perchlorate, sulfate, phosphate, nitrate and carboxylates, such as acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, as well as conjugated anions of organosulfonic acids, such as methyl sulfonate , Trifluoromethylsulfonate and para-toluenesulfonate, furthermore tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyl) borate, tetrakis [
  • the emulsifiers preferably used as dispersing agents are advantageously in a total amount ⁇ 0.005 and ⁇ 10 wt .-%, preferably ⁇ 0.01 and ⁇ 5 wt .-%, in particular ⁇ 0.1 and ⁇ 3 wt .-%, each based on the total amount of monomers used.
  • the total amount of the protective colloids used as dispersing agents in addition to or instead of the emulsifiers is often ⁇ 0.1 and ⁇ 10% by weight and frequently ⁇ 0.2 and ⁇ 7% by weight, in each case based on the total monomers.
  • anionic and / or nonionic emulsifiers preference is given to using anionic and / or nonionic emulsifiers and, with particular preference, anionic emulsifiers as dispersion auxiliaries.
  • the total amount of the dispersing aid in the aqueous reaction medium can be initially introduced before the initiation of the polymerization reaction.
  • the addition of the main or the total amount of dispersing aid takes place in the form of an aqueous monomer emulsion.
  • free-radical polymerization initiator can be both peroxides and azo compounds.
  • redox initiator systems come into consideration.
  • peroxides may in principle inorganic peroxides, such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of peroxodisulfuric, such as their mono- and di-sodium, - potassium or ammonium salts or organic peroxides, such as alkyl hydroperoxides, for example tert-butyl, p-menthyl or cumyl hydroperoxide, as well as dialkyl or diarylperoxides, such as di-tert-butyl or di-cumyl peroxide are used.
  • inorganic peroxides such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of peroxodisulfuric, such as their mono- and di-sodium, - potassium or ammonium salts or organic peroxides, such as alkyl hydroperoxides, for example
  • the azo compounds are essentially 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (amidinopropyl) dihydrochloride (AIBA, corresponding to V-50 from Wako Chemicals). Use.
  • Suitable oxidizing agents for redox initiator systems are essentially the abovementioned peroxides.
  • Suitable reducing agents may be sulfur compounds having a low oxidation state, such as alkali metal sulfites, for example potassium and / or sodium sulfite, alkali hydrogen sulfites, for example potassium and / or sodium hydrogen sulfite, alkali metal metabisulfites, for example potassium and / or sodium metabisulfite, formaldehyde sulfoxylates, for example potassium and / or sodium formaldehyde sulfoxylate, alkali metal salts, especially potassium and / or sodium salts, aliphatic sulfinic acids and alkali metal hydrogen sulfides, such as potassium and / or sodium hydrosulfide, salts of polyvalent metals, such as iron (II) sulfate, iron (II) ammonium sulfate, iron (II) phosphate, Endiols, such as dihydroxymaleic acid, benzoin and / or ascorbic acid and reducing saccharides
  • the total amount of the radical initiator in the aqueous reaction medium before initiation of the polymerization reaction can be presented.
  • Initiation of the polymerization reaction is understood to mean the start of the polymerization reaction of the monomers present in the polymerization vessel after radical formation of the radical initiator.
  • the initiation of the polymerization reaction by adding radical initiator to the aqueous polymerization mixture in the polymerization vessel can be carried out under polymerization conditions.
  • a partial or total amount of the radical initiator is added to the aqueous polymerization mixture containing the monomers present in the polymerization vessel under conditions which are not suitable for initiating a polymerization reaction, for example at low temperature, and polymerization conditions are subsequently set in the aqueous polymerization mixture .
  • Polymerization conditions are to be understood as meaning in general those temperatures and pressures under which the free-radically initiated aqueous emulsion polymerization proceeds at a sufficient rate of polymerization. They are dependent, in particular, on the radical initiator used.
  • the type and amount of the radical initiator, the polymerization temperature and the polymerization pressure are advantageously selected so that the free-radical initiator has a half-life of ⁇ 3 hours, more preferably ⁇ 1 hour and most preferably ⁇ 30 minutes, and there are always enough starting radicals available to effect the polymerization reaction to initiate and maintain.
  • the reaction temperature for the free-radical aqueous emulsion polymerization according to the invention is the entire range from 0 to 170 ° C into consideration. In this case, temperatures of 50 to 120 ° C, often 60 to 110 ° C and often 70 to 100 ° C are usually applied.
  • the free-radical aqueous emulsion polymerization according to the invention can be carried out at a pressure of less than or equal to 1 atm [1.013 bar (absolute), atmospheric pressure], such that the polymerization temperature can exceed 100 ° C. and can be up to 170 ° C.
  • polymerization is preferably carried out under elevated pressure in the process according to the invention.
  • the pressure can be 1,2, 1,5, 2, 5, 10, 15 bar (absolute) or even higher values. If emulsion polymerizations are carried out under reduced pressure, pressures of 950 mbar, often 900 mbar and often 850 mbar (absolute) are set.
  • the free-radical aqueous emulsion polymerization according to the invention is advantageously carried out at 1 atm or in overpressure up to 20 bar with exclusion of oxygen, in particular under an inert gas atmosphere, for example under nitrogen or argon.
  • the aqueous reaction medium may in principle also in minor amounts ( ⁇ 5 wt .-%) include water-soluble organic solvents such as methanol, ethanol, isopropanol, butanols, pentanols, but also acetone, etc.
  • water-soluble organic solvents such as methanol, ethanol, isopropanol, butanols, pentanols, but also acetone, etc.
  • the process according to the invention is preferably carried out in the absence of such solvents.
  • free radical-transferring compounds in the process according to the invention in order to reduce or control the molecular weight of the polymers obtainable by the polymerization.
  • These are essentially aliphatic and / or araliphatic halogen compounds, such as n-butyl chloride, n-butyl bromide, n-butyl iodide, methylene chloride, ethylene dichloride, chloroform, bromoform, bromotrichloromethane, Dibromdichlormethan, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide, organic thio compounds such as primary , secondary or tertiary aliphatic thiols such as ethanethiol, n-propanethiol, 2-propanethiol, n-butanethiol, 2-butanethiol, 2-methyl-2
  • the total amount of radical chain-transferring compounds optionally used in the process according to the invention is generally ⁇ 5% by weight, often ⁇ 3% by weight and frequently ⁇ 1% by weight.
  • a partial or total amount of the radical chain transferring compound optionally used is fed to the reaction medium before the initiation of the free-radical polymerization.
  • a partial or total amount of the radical chain transferring compound can advantageously also be fed to the aqueous reaction medium together with the monomers A1 to A4 during the polymerization.
  • the polymers A obtainable by the process according to the invention can in principle have glass transition temperatures Tg in the range of ⁇ -70 and ⁇ 150 ° C.
  • the monomers A1 to A4 are advantageously selected so that the resulting polymers A have a glass transition temperature Tg in the range of ⁇ -10 and ⁇ 130 ° C and particularly advantageously in the range ⁇ 10 and ⁇ 100 ° C.
  • glass transition temperature Tg is understood to mean the midpoint temperature according to ASTM D 3418-82, determined by differential thermal analysis (DSC) [cf. also Ullmann's Encyclopedia of Industrial Chemistry, page 169, Verlag Chemie, Weinheim, 1992 and Zosel in paint and varnish, 82, pages 125 to 134, 1976 ].
  • the free-radically initiated aqueous emulsion polymerization according to the invention can advantageously also be carried out in the presence of a polymer seed, for example in the presence of from 0.01 to 3% by weight, frequently from 0.02 to 2% by weight and often from 0.04 to 1.5% by weight .-% of a polymer seed, in each case based on the total amount of monomers, take place.
  • a polymer seed is used in particular if the particle size of the polymer particles to be produced by means of a free-radically aqueous emulsion polymerization is to be adjusted in a targeted manner (see, for example, for this US-A 2520959 and US-A 3397165 ).
  • a polymer seed is used whose polymer seed particles have a narrow particle size distribution and weight-average diameters Dw ⁇ 100 nm, frequently ⁇ 5 nm to ⁇ 50 nm and often ⁇ 15 nm to ⁇ 35 nm.
  • the determination of the weight-average particle diameter is known to the person skilled in the art and is carried out, for example, by the method of the analytical ultracentrifuge.
  • Weight-average particle diameter in this document is understood to mean the weight-average Dw50 value determined by the method of the analytical ultracentrifuge (cf.
  • a narrow particle size distribution should be understood within the scope of this document if the ratio of the weight-average particle diameter Dw50 determined by the analytical ultracentrifuge method and the number-average particle diameter DN50 [Dw50 / DN50] ⁇ 2.0, preferably ⁇ 1.5 and particularly preferably ⁇ 1, 2 or ⁇ 1.1.
  • the polymer seed is used in the form of an aqueous polymer dispersion.
  • the aforementioned amounts are based on the polymer solids content of the aqueous polymer seed dispersion.
  • a polymer seed is understood to mean a polymer seed, which was prepared in a separate reaction step and the monomeric composition of which is different from the polymer prepared by the free-radically initiated aqueous emulsion polymerization, which means nothing else than that for the preparation of Fremdpolymersaat and for preparing the aqueous polymer dispersion different monomers or monomer mixtures of different composition be used.
  • the preparation of a foreign polymer seed is familiar to the person skilled in the art and is usually carried out by initially charging a relatively small amount of monomers and a relatively large amount of emulsifiers in a reaction vessel and adding a sufficient amount of polymerization initiator at reaction temperature.
  • a foreign metal seed having a glass transition temperature ⁇ 50 ° C., frequently ⁇ 60 ° C. or ⁇ 70 ° C. and often ⁇ 80 ° C. or ⁇ 90 ° C. is preferably used.
  • Particularly preferred is a polystyrene or polymethyl methacrylate polymer seed.
  • the total amount of foreign polymer seed can be presented in the polymerization vessel. But it is also possible to submit only a subset of Fremdpolymerse seed in the polymerization and the remaining amount during the polymerization together with the monomers A1 to A4. If necessary, however, it is also possible to add the total amount of polymer seed in the course of the polymerization. Preferably, the total amount of Fremdpolymersaat is submitted before initiation of the polymerization in the polymerization.
  • the aqueous polymer A dispersions obtainable according to the invention usually have a polymer solids content of ⁇ 10 and ⁇ 70% by weight, frequently ⁇ 20 and ⁇ 65% by weight and often ⁇ 25 and ⁇ 60% by weight, based in each case on the aqueous Polymerisate, on.
  • the number-average particle diameter (cumulant z-average) determined by quasi-elastic light scattering (ISO standard 13 321) is generally between 10 and 2000 nm, frequently between 20 and 1000 nm and often between 100 and 700 nm and 100 to 400 nm.
  • aqueous polymer A dispersions obtainable by the process according to the invention can in principle be used for the production of adhesives, sealants, plastic plasters, paper coating slips, fiber webs, paints and coating compositions for organic substrates, such as leather or textile materials, and for the modification of mineral binders.
  • aqueous polymer A dispersions obtainable by the process according to the invention are particularly advantageously suitable for use as binders for granular and / or fibrous substrates.
  • the abovementioned aqueous polymer A dispersions can therefore advantageously be used for the production of moldings from granular and / or fibrous substrates.
  • Granular and / or fibrous substrates are familiar to the person skilled in the art.
  • these are wood chips, wood fibers, cellulose fibers, textile fibers, plastic fibers, glass fibers, mineral fibers or natural fibers such as jute, flax, hemp or sisal, but also cork chips, sand and others
  • Organic or inorganic natural and / or synthetic granular and / or fibrous compounds whose longest extent in the case of granular substrates ⁇ 10 mm, preferably ⁇ 5 mm and in particular ⁇ 2 mm.
  • substrate according to the invention should also include the fiber webs obtainable from fibers, such as so-called mechanically bonded or chemically pre-bonded nonwoven fabrics and mechanically consolidated or chemically pre-bonded papers (in particular base papers and glued papers) and in particular also porous filter papers.
  • base paper (basis weight ⁇ 225 g / m 2 ) or of raw board (basis weight> 225 g / m 2 ).
  • cardboard is also common, which comprises a basis weight of about 150 to 600 g / m 2 both base paper grades and raw paperboard.
  • base paper will be understood to include both base paper, raw board and cardboard.
  • raw paper surfaces are treated with sizing agents, which essentially influence the absorbency and thus the writing or printability of the raw paper.
  • the papers treated in this way are called "glued papers”.
  • Corresponding methods and the type and amounts of the corresponding sizing agents are familiar to the person skilled in the art.
  • the base paper or glued paper is refined by the so-called brushing, or transferred to the finished form of use.
  • coating of paper is understood to mean the one- or two-sided coating of the paper with an aqueous coating material consisting essentially of pigments and binders. Depending on the type of coating color, the layer thickness to be achieved or the type of paper to be produced, this will be the case different coating methods, for example, the known in the art roller, doctor blade, air brushing or casting coating used, which in each case followed by a drying step.
  • the papers treated in this way are called “coated papers”.
  • novel aqueous polymer A dispersion is particularly advantageously suitable as a formaldehyde-free binder system for the abovementioned fibers or fiber webs or papers formed therefrom.
  • novel aqueous polymer A dispersions are used as sole or as an additional binder or binder component for the reinforcement of base paper and for sized paper, but in particular for filter paper.
  • the process for producing a shaped body from a granular and / or fibrous substrate and the abovementioned aqueous polymer A dispersion or a binder formulation containing these advantageously takes place such that the inventive aqueous polymer A dispersion or a binder formulation containing them on the granular and / or fibrous substrate is applied or the granular and / or fibrous substrate is impregnated with the aqueous polymer A dispersion according to the invention or a binder formulation containing them, optionally the treated with the aqueous polymer A dispersion or a binder formulation containing granular and / or fibrous substrate is brought into shape and the thus treated granular and / or fibrous substrate are then subjected to a thermal treatment step at a temperature ⁇ 50 ° C.
  • Aqueous binder formulations which contain an aqueous polymer dispersion A according to the invention may comprise further customary auxiliaries known to the person skilled in the art, such as fillers, dyes, pigments, optical brighteners, retention aids, wetting agents, defoamers, preservatives, slimicides, plasticizers, Antiblocking agents, antistatic agents, water repellents, etc.
  • auxiliaries known to the person skilled in the art, such as fillers, dyes, pigments, optical brighteners, retention aids, wetting agents, defoamers, preservatives, slimicides, plasticizers, Antiblocking agents, antistatic agents, water repellents, etc.
  • the application (impregnation) of the aqueous polymer A dispersion according to the invention or a binder formulation containing these to the granular and / or fibrous substrate is generally carried out in such a way that the novel aqueous polymer A dispersion or a binder formulation containing the same uniformly on the surface of the granular and / or fibrous substrate is applied.
  • the amount of aqueous polymer A dispersion or aqueous binder formulation is chosen such that per 100 g of granular and / or fibrous substrate ⁇ 1 g and ⁇ 100 g, preferably ⁇ 1 g and ⁇ 50 g and particularly preferably ⁇ 5 g and ⁇ 30 g of polymer A (calculated as a solid) are used.
  • the technique of impregnating the granular and / or fibrous substrates is familiar to the person skilled in the art and takes place, for example, by impregnation or by spraying the granular and / or fibrous substrates.
  • the granular and / or fibrous substrate is optionally brought into the desired shape, for example by introduction into a heatable press or mold. Thereafter, the shaped impregnated granular and / or fibrous substrate is dried and cured in a manner known to those skilled in the art.
  • the drying and curing of the optionally shaped impregnated granular and / or fibrous substrate is carried out at a temperature of ⁇ 50 ° C and ⁇ 250 ° C, preferably ⁇ 100 ° C and ⁇ 220 ° C and more preferably ⁇ 150 and ⁇ 200 ° C.
  • the moldings obtainable by the process according to the invention in particular non-woven fabrics or papers, have advantageous properties, in particular improved tear strength or increased bursting pressure, in comparison to the moldings of the prior art.
  • Feed 1 consisted of a homogeneous emulsion prepared from 396 g of deionized water, 46.7 g of a 3% strength by weight aqueous sodium pyrophosphate solution, 6.2 g of a 45% strength by weight aqueous solution of a C 12 -C 14 -alkyldiphenyl ether- Disulfonic acid sodium salt (Dowfax® 2A1), 50.0 g of a 28 wt .-% aqueous solution of sodium lauryl ether sulfate (Texapon® NSO Cognis), 68.6 g of acrylic acid, 46.7 g of a 15 wt .-% aqueous solution of methacrylamide, 23.5 g of glycidyl methacrylate, 734 g of styrene and 567 g of n-butyl acrylate.
  • Dowfax® 2A1 a C 12 -C 14 -alkyldipheny
  • Feed 2 consisted of 110 g of a 7% strength by weight aqueous solution of sodium peroxodisulfate.
  • the original was heated to 95 ° C. with stirring and nitrogen atmosphere. Subsequently, while maintaining this temperature, 33.0 g of feed 2 were added and the original was stirred for 5 minutes. Subsequently, feed 1 was added simultaneously within 135 minutes and the remainder of feed 2 was metered in over the course of 140 minutes at constant flow rates.
  • aqueous polymer dispersion After completion of the feeds was polymerized for a further 15 minutes at 95 ° C and then cooled, the resulting aqueous polymer dispersion to 75 ° C. At this temperature, starting simultaneously 35.0 g of a 10 wt .-% aqueous tert-butyl hydroperoxide solution and 42.1 g of a 13.3 wt .-% aqueous solution of acetone bisulfite (molar 1: 1 addition of Acetone and sodium hydrogen sulfite) within 60 minutes with constant flow rates metered. After completion of the doses, the aqueous polymer dispersion was cooled to room temperature.
  • the solids contents were generally determined by adding a defined amount of the aqueous polymer dispersion (about 0.8 g) using moisture analyzer HR73 from Mettler Toledo was dried at a temperature of 130 ° C to constant weight.
  • the number average particle diameter of the latex particles was determined by dynamic light scattering (DLS) on a 0.005 to 0.01 weight percent aqueous dispersion at 23 ° C. by means of Autosizer IIC from Malvern Instruments, England.
  • the mean diameter of the cumulant evaluation (cumulant z-average) of the measured autocorrelation function (ISO standard 13321) is given.
  • the glass transition temperature was determined using a differential calorimeter from Mettler Toledo. The heating rate was 10K / min. The evaluation was carried out by means of the software Star Version 9.01.
  • Example 2 The preparation of Example 2 was carried out completely analogously to Example 1, but with the difference that in feed 1 393 g instead of 396 g of deionized water, 26.3 g of a 50 wt .-% aqueous solution of acrylamide instead of 46.7 g a 15 wt .-% aqueous solution of methacrylamide and 728 g instead of 734 g of styrene were used.
  • the aqueous polymer dispersion obtained had a solids content of 50.2% by weight.
  • the number average particle size was determined to be 172 nm and the Tg to 39 ° C.
  • Example 3 The preparation of Example 3 was completely analogous to Example 1, but with the difference that in feed 1 266 g instead of 396 g of deionized water, 175 g instead of 46.7 g of a 15 wt .-% aqueous solution of methacrylamide and 715th g were used instead of 734 g of styrene.
  • the aqueous polymer dispersion obtained had a solids content of 50.5% by weight.
  • the number average particle size was determined to be 179 nm and the Tg to 39 ° C.
  • Example 4 The preparation of Example 4 was completely analogous to Example 1, but with the difference that in feed 1 158 g instead of 396 g of deionized water, 327 g instead of 46.7 g of a 15 wt .-% aqueous solution of methacrylamide and 692nd g were used instead of 734 g of styrene.
  • the aqueous polymer dispersion obtained had a solids content of 49.1% by weight.
  • the number average particle size was determined to be 178 nm and the Tg to 39 ° C.
  • Comparative Example C1 The preparation of Comparative Example C1 was carried out completely analogously to Example 1, but with the difference that in feed 1 436 g instead of 396 g of deionized water, 741 g instead of 734 g of styrene and no methacrylamide were used.
  • the aqueous polymer dispersion obtained had a solids content of 49.6% by weight.
  • the number average particle size was found to be 175 nm and the Tg to 40 ° C.
  • Comparative Example C2 The preparation of Comparative Example C2 was carried out completely analogously to Example 1, but with the difference that in feed 1 757 g instead of 734 g of styrene and no glycidyl methacrylate were used.
  • the aqueous polymer dispersion obtained had a solids content of 50.2% by weight.
  • the number average particle size was determined to be 184 nm and the Tg to 41 ° C.
  • Comparative Example V3 was carried out completely analogously to Example 1, but with the difference that in feed 1 802 g instead of 734 g of styrene and no acrylic acid were used.
  • the aqueous polymer dispersion obtained had a solids content of 49.8% by weight.
  • the number average particle size was determined to be 168 nm and the Tg to 42 ° C.
  • a commercial base paper for the production of automobile air filters with a basis weight of 107 g / m 2 was used.
  • the paper sheets had a size of 21.0 x 29.7 cm [A4], with the longitudinal direction of the machine direction corresponded.
  • the aqueous polymer dispersions obtained according to Examples 1 to 4 and Comparative Examples C1 to V3 were diluted with deionized water to a solids content of 10% by weight. Thereafter, the aforementioned paper sheets were passed in the longitudinal direction through an endless belt at a belt speed of 80 cm per minute through the thus obtained binder baths 1 to 4 and V1 to V3. By subsequent extraction of the binder liquors, a wet application of 210 g / m 2 (corresponding to 21 g of polymer per m 2 ) was set. Thereafter, the wet paper sheets were dried for 3 minutes at 180 ° C in a Mathis oven at maximum hot air flow. Thereafter, the impregnated papers thus obtained were stored for 24 hours at 23 ° C and 50% RH in a climatic room.
  • test strips 1 to 4 and test strips V1 to V3 20 x 15 cm test strips were cut out of the impregnated papers.
  • aqueous polymer dispersions used for impregnation 1 to 4 and V1 to V3, these are referred to as test strips 1 to 4 and test strips V1 to V3.
  • the test strips were incubated for 2 minutes in a 2 wt .-% aqueous solution of emulsifier ® K30 (sodium alkanesulfonate having an average chain length of 15 C; Bayer AG) stored, blotted excess emulsifier with a cotton fabric and immediately after the burst pressure (wet) determined with a strength testing machine from Zwick with the test module bursting pressure according to ISO 2758.
  • emulsifier ® K30 sodium alkanesulfonate having an average chain length of 15 C; Bayer AG

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